US3373143A - Manufacture of polyurethane solutions - Google Patents

Manufacture of polyurethane solutions Download PDF

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Publication number
US3373143A
US3373143A US28287563A US3373143A US 3373143 A US3373143 A US 3373143A US 28287563 A US28287563 A US 28287563A US 3373143 A US3373143 A US 3373143A
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Prior art keywords
parts
solution
isocyanate
diisocyanate
polyurethane
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Chilvers Kenneth William
Crowley Gerald Patrick
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
    • C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/302—Water
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/60—Polyamides or polyester-amides
    • C08G18/606—Polyester-amides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S528/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S528/905—Polymer prepared from isocyanate reactant has adhesive property
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31554—Next to second layer of polyamidoester
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
    • Y10T428/3158—Halide monomer type [polyvinyl chloride, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]

Definitions

  • ABSTRACT OF THE DISCLOSURE A process for obtaining solutions of polyurethanes in organic solvents, suitable for preparing elastomeric films, coatings, and adhesives, by interaction in an inert solvent of a hydroxyl-terminated compound and excess diisocyanate in presence of a controlled small quantity of water, and thereafter adding isocyanate reactive compounds to remove residual free isocyanate groups.
  • This invention relate to an improved process for the manufacture of solutions of polyurethanes.
  • Polyurethane elastomers obtained from polymeric hydroxyl-terminated compounds such as polyesters and polyester-amides by reaction with approximately equivalent amounts of diisocyanates, may be dissolved in organic solvents such as esters, ketones or aromatic hydrocarbons.
  • organic solvents such as esters, ketones or aromatic hydrocarbons.
  • the process of dissolving the polyurethane is however not attractive since a prolonged time of mixing in heavy duty equipment is usually required.
  • the properties, in particular viscosity, of the solutions obtained are critically dependent upon the degree of chain extension in the preparation of the polyurethane elastomer and the reproducible preparation of these solutions requires a degree of control in the manufacture of the polyurethane which it is difficult to exercise.
  • Attempts to prepare the polyure' thanes in solution by interaction of the polymeric hydroxyl-terminated compounds and diisocyanates in a solvent have hitherto led to solutions of low viscosity which have little practical utility.
  • solutions of polyurethanes in organic solvents suitable for use in the manufacture of elastomeric films, coatings and adhesives, may be obtained by interaction in an inert organic solvent of a hydroxyl-terminated compound and excess diisocyanate in presence of a controlled small quantity of water. Under these conditions solutions of suitably high viscosity can be obtained which can be stabilized against further viscosity increase by removal of residual free isocyanate groups by the addition of isocyanate-reactive compounds.
  • a process for the manufacture of a solution in an inert organic solvent of a polyurethane which comprises the steps of (1) interacting in said solution, 1 molar proportion of a hydroxyl-terminated polyester or polyesteramide, between 1.2 and 2.5 molar proportions of an organic diisocyanate and between 0.25 and 1.0 molar proportions of water and, when the viscosity of the solution is between 1 and 1500 poiscs measured at 25 C. (2) adding an isocyanate-reactive compound in molar amount at least substantially equal to the molar amount of isocyanate groups unreacted at the end of step (1).
  • organic solvent there may be mentioned any organic solvent which is inert towards isocyanate and hydroxyl groups, preferred solvents being esters, ketones, aromatic hydrocarbons, and chlorohydrocarbons.
  • the amount of solvent should be suflicient to give solutions containing from to 80% of polyurethane.
  • the hydroxyl-terminated polyester or polyesteramide used in the process of our invention should be essentially linear and prepared by conventional methods from for example dicarboxylic acids, glycols and, as necessary, minor proportions of diamines or aminoalcohols.
  • Suitable dicarboxylic acids include succinic, glutaric, adipic, suberic, azelaic, sebacic, phthalic, isophthalic and terephthalic acids and mixtures of these.
  • dihydric alcohols examples include ethylene glycol, 1:2-propyleneglycol, 1:3-buty1ene glycol, 2:3-butyleneglycol, diethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol and 2:2-dimethyltrimethyleneglycol.
  • Suitable diamines or aminoalcohols include hexamethylene diamine, ethylene diamine, monoethanolamine, phenylenediamines and benzidine. Mixtures of polyesters and polyesteramides may be used if desired.
  • polyesters and polyesteramides should preferably have acid value less than 5 mg. KOH/ g. and a molecular weight between 800 and 5000, and preferably between 1000 and 2700.
  • polyesterarnides containing one amido group for each 1500 to 12,000 units of molecular weight are used.
  • the preferred quantities of diisocyanate and water for reaciton with one mol. of such a polyesteramide are between 1.3 and 1.6 mol. of diisocyanate and between 0.3 and 0.6 mol. of water.
  • suitable organic diisocyanates include aliphatic diisocyanates such as hexamethylene diisocyanate, aromatic diisocyanates such as tolylene-2:4-diisocyanate, tolylene-Z:6-diisocyanate, diphenylmethane-4:4-diisocyanate, 3-methyldiphenylmethane-4:4'-diisocyanate, mand p-phenylenediisocyanate, chlorophenylene 2:4 diisocynate, naphthylene-l :S-diisocyanate, naphthylene-1t4-diisocyanate, diphenyl-4:4-diisocyanate, 4:4-diisocyanate- 3:3'-dimethyldiphenyl, diphenylether diisocyanates, and cycloaliphatic diisocyanates such as dicyclohexylmethane diisocyanate, and cycl
  • the isocyanate-reactive compound there may be mentioned for example any compound containing hydroxyl, or primary or secondary amino groups.
  • the isocyanatereactive compound may be monofunctional, as for example an alcohol such as methanol, phenol, or primary or secondary monoamine, or polyfunctional as for example ethylene glycol, diethylene glycol, 2:3-butylene glycol, tetramethylene glycol, trimethylolpropone, ethylene diamine, hexamethylene diamine, N:N-disubstituted ethylene diamines, phenylene diamines, tolylenediamines, and diaminodiphenylmethane.
  • an alcohol such as methanol, phenol, or primary or secondary monoamine
  • polyfunctional as for example ethylene glycol, diethylene glycol, 2:3-butylene glycol, tetramethylene glycol, trimethylolpropone, ethylene diamine, hexamethylene diamine, N:N-disubstituted
  • Water also functions as a difuctional isocyanate-reactive compound in the process of the invention. It is preferred to use polyfunctional isocyanate-reactive compounds since they lead to surface-coatings and adhesives of improved properties. Of the organic polyfunctional isocyanate-reactive compounds, it is preferred to use compounds in which the reactive groups are not all of the same reactivity towards the isocyanate group as for example in 1:2-propyleneglycol, glycerol, 1:3- butylene glycol, ethanolamine and diethanolamine since these compounds give a better control of the viscosity.
  • the amount of isocyanate-reactive compound needed will depend upon the amount of unreacted isocyanate groups which Wiil vary with the polyesters or polyesteramides and diisocyanates used and amounts of these and also the extent to which it is necessary to carry out reaction in order to achieve the required viscosity.
  • the amount of unreacted isocyanate groups can be determined by conventional methods and the necessary minimum 3 trsage of isocyanate-reactive compound then calculated on the basis of a molar amount for each molar amount of free isocyanate groups, i.e. so that for each isocyanate group there is one molecule of isocyanate-reactive compound.
  • the isocyanate-reactive compound contains primary or secondary amino groups it is desirable to deactivate any excess for example by treatment with a reactive ester such as diethyl carbonate as the primary or secondary amino groups may cause some degradation of the polyester part of the Polyurethane.
  • Step (1) of the process of the invention may be carried out at any temperature between 40 and 130 C. but temperatures between 60 and 100 are preferred. It may however be desirable to reduce the temperature to below these ranges near the end of the reaction in order to facilitate control of the reaction.
  • catalysts of the types used in reactions between isocyanates and compounds containing active hydrogen such as organic and inorganic basic compounds, and soluble organic compounds of metals, for example of transition metals, 'such as iron and manganese acetyl acetonate, and of tin and antimony, for example dibutyl tin dilaurate and stannous octoate, compounds of lead such as lead acetate, basic lead acetate and lead 2-ethylhexoate.
  • transition metals such as iron and manganese acetyl acetonate
  • tin and antimony for example dibutyl tin dilaurate and stannous octoate
  • compounds of lead such as lead acetate, basic lead acetate and lead 2-ethylhexoate.
  • basic organic catalyst tertiary amines are suitable, particularly 4-dimethylaminopyridine, triethylenediamine, dimethylbenzylamine, and dimethylcyclohex
  • Step (2) of the process of the invention may be carried out at any temperature, from room temperature to a temperature of 130 C.
  • an acidic compound is desirable, since such catalysts if left in the reaction mixture may give rise to shortened storage life or pot life at the application stage.
  • suitable acidic compounds include organic acids, such as adipic acid, salicylic acid and inorganic acids such as phosphoric acid or hydrochloric acid.
  • the solutions prepared by the process of our invention are of especial value in the manufacture of flexible coatings andfadhesives.
  • Substrates for these include textiles of natural, artificial or synthetic materials, rubber, paper, wood, leather, metals, glass, plastics such as polyvinyl chloride and polyurethane materials such as flexible and rigid foams.
  • Such solutions are particularly advantageous when used as adhesives in the lamination of plastic sheet material to a substrate.
  • substrates are knitted, woven or felted materials, flexible and rigid foams made from polyvinyl chloride or polyurethane. Hitherto, the lamination of plastic materials to such substrates has been found difficult to achieve.
  • a permanent bond may be made between these materials by conventional laminating techniques.
  • organic polyisocyanates which may contain two or more isocyanate groups, applied to the substrates by any conventional method, and the coatings so obtained are cured at any temperature between room temperature and 180 C.
  • Organic polyisocyanates which may be used for curing include those known from the prior art to be useful for the preparation of polyurethanes, for example those diisocyanates mentioned above as suitable for the preparation of the polyurethane solution. Polyisocyanates containing more than two isocyanate groups per molecule may however be used.
  • polyisocyanates examples include the reaction products of an excess of diisocyanate with trihydric alcohols or mixtures of dihydric and trihydric alcohols, isocyanate group-containing isocyanurate polymers of diisocyanates and polyisocyanates, as well as aromatic tn'isocyanates such as 2:4:4-.
  • triisocyanatodiphenylether and 2:416 -triisocyanatotoluene The proportion of polyisocyanate used for curingiS desirably from about 8% to 25% by weight of the solids content of the polyurethane solution, but amounts out; side this range may be used if desired, especially if an excess of isocyanate-reactive compound is used for stabilisation.
  • curing temperatures preferably should be between room temperature and C.
  • lsoeyanate generators such as adducts of polyisocyanates with phenols may also be used in which case curing temperatures between 70 C. and C. are necessary.
  • the polyurethane solutions may also be converted, preferably after the addition of further polyisocyanate, into elastomeric filaments by conventional wet or dry spinning methods.
  • the inert organic solvent may for example be removed by spinning into a solvent which is miscible with the inert organic solvent but is not a solvent for the prepolymer or by passing a stream of hot gas such as air over the filament after spinning.
  • Example 1 27.6 parts of an 80/20 mixture'of 2:4: and 2:6-tolylene diisocyanate and 0.6 part of water are added to 500 parts by volume of a solution in methylethyl ketone of 200 parts by Weight of a polyesteramide, and the mixture is heated at 80 C. precautions being taken to ensure no contact with atmosphereic moisture. The viscosity of the solution rises slowly and after 42 hours, when it has reached about 200 poises at 25 C. the solution is cooled and a solution of 2.1 parts by weight of methanol in 7 parts of methylehtyl ketone is added with stirring. The solution so obtained is suitable for the preparation of surface coatings as described in Example 3..
  • the polyesteramide used in this example is prepared by heating a mixture of 176 parts of ethylene glycol, 17.1- parts of diethylene glycol, 11.0 parts of ethanolamine and 420 parts of adipic acid at 240 C. and has an acid value of 2.0 and hydroxyl value of 57.3.
  • Example 2 25.2 parts by Weight of an 80:20 mixture of 2.4 and 2:6-tolylene diisocyanate are added to. a solution con taining 200 parts of a polyestera-mide, 0.8 part water,v 02 part 4-dimethylaminopyridine and 370 parts of methylethylketone previously heated to 601 C under a nitrogen atmosphere. The solution is then heated to a temperature between 79 to 80 C. and held at that temperature for 716 hours, when the viscosity of a sample diluted with 0.875 of i-tsweight of methylethyl ketone has reached a minimum of 1.2 poise at 25 C. The solution is cooled to 60 C. and 3.5 parts of methanol are added. After stirring for a further 30 minutes 0.2 part of salicyclic acid dissolved in 3.5 parts of methylethylketone are added and the mixture is stirred until fully homogeneous.
  • the polyester-amide used in this example is prepared by heating a mixture of 176 parts of ethylene glycol, 17.1 parts of diethylene glycol, 11.0 parts of ethanolamine and 420 parts of adipic acid at 240 C. and has an acid value of 2.0 and hydroxyl value of 57.3.
  • Example 3 9 parts of a 75% polyisocyanate solution in ethyl acetate, prepared by interacting an 80:20 mixture of 2:4- and 2:6-tolylenediisocyanates with a mixture of glycerol in ethyl acetate in amount so that there is 1 molar equivalent of diisocyanate for each hydroxyl group, are added to 100 parts of the solution prepared as described in Example 1.
  • the mixture so obtained is spread on a nylon textile fabric and allowed to cure at room temperature for 3 days.
  • a coating is obtained which has good adhesion and which is resistant to abrasion and dry-cleaning solvents.
  • Example 5 The procedure of Example 4 is repeated using 3.5 parts of propylene glycol in place of the 2.7 parts of ethylene glycol. A solution is obtained which is of similar utility to that prepared in Example 4.
  • the isocyanate composition used in this example is prepared by phosgenation of crude 4:4-diamino-3- methyldiphenylmethane containing about 15% of polyamines obtained by condensing aniline, ortho-toluidine and formaldehyde in the molar proportions 3.3:1.1:1.0 in presence of hydrogen chloride.
  • a process for the manufacture of a solution in an inert organic solvent of a polyurethane which comprises the steps of (1) interacting while dissolved in said solvent 1 molar proportion of a member selected from the group consisting of hydroxyl-terminated polyester and polyesteramide, between 1.2 and 2.5 molar proportions of an organic diisocy-anate and between 0.25 and 1.0 molar proportions of water and, when the viscosity of the solution is between 1 and 1500 poises measured at 25 C.
  • step 2 (2) adding an isocyanatereactive compound selected from the group consisting of water and monofunctional and polyfunctional alcohols, phenols and primary and secondary amines in molar amount at least substantially equal to the molar amount of isocyanate groups unreacted at the end of step 1).
  • an isocyanatereactive compound selected from the group consisting of water and monofunctional and polyfunctional alcohols, phenols and primary and secondary amines in molar amount at least substantially equal to the molar amount of isocyanate groups unreacted at the end of step 1).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)
US28287563 1962-05-30 1963-05-24 Manufacture of polyurethane solutions Expired - Lifetime US3373143A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB2085662A GB1044155A (en) 1962-05-30 1962-05-30 Manufacture of polyurethane solutions
GB2085663 1963-05-16

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US3373143A true US3373143A (en) 1968-03-12

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3503934A (en) * 1962-05-30 1970-03-31 Ici Ltd Manufacture of polyurethane solutions
US3535287A (en) * 1965-06-03 1970-10-20 Union Carbide Corp Polyurethanes based on three-component polyester oligomers
US3915923A (en) * 1970-10-26 1975-10-28 Union Carbide Corp Solution process for making polyurethane
US3948847A (en) * 1968-04-29 1976-04-06 Imperial Chemical Industries Limited Process for the manufacture of polymer solutions
US3997645A (en) * 1974-10-08 1976-12-14 Canathane Roller Corporation Method of rotational molding a rectangular mat
US4010311A (en) * 1973-09-14 1977-03-01 Ppg Industries, Inc. Impact-resistant glass-polyesterurethane laminates
US4166873A (en) * 1974-09-16 1979-09-04 Standard Oil Company (Indiana) Diisocyanate-modified polyesters as hot melt adhesives and coatings
US4317895A (en) * 1979-01-02 1982-03-02 Inmont Corporation Coating compositions of thermoplastic acrylic-urethane copolymers
US4324716A (en) * 1976-08-27 1982-04-13 Bayer Aktiengesellschaft Solutions of polyisocyanate polyaddition products
US4442259A (en) * 1982-04-26 1984-04-10 W. R. Grace & Co. Aqueous-based polyurethane compositions and method of preparation
US4734310A (en) * 1985-05-28 1988-03-29 Solvay & Cie Sheet of artificial leather made of polyvinyl chloride, the back of which is coated with a dry adhesive capable of being activated by heat, and use of this sheet for thermocovering of rigid articles
US5143995A (en) * 1990-07-03 1992-09-01 Bayer Aktiengesellschaft Adhesives based on polyols and polyisocyanates

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2500921C3 (de) * 1975-01-11 1986-10-23 Basf Ag, 6700 Ludwigshafen Verfahren zur Herstellung von Polyurethanlösungen
DE2832759A1 (de) * 1978-07-26 1980-02-14 Basf Ag Verfahren zur herstellung von hochmolekularen, in organischen loesungsmitteln loeslichen polyurethanen

Citations (14)

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US2729618A (en) * 1952-11-18 1956-01-03 Bayer Ag Isocyanate-modified polyesters reacted with glycols
CA538977A (en) * 1957-04-02 S. Carter Albert Preparing polyether-diisocyanate elastomers in organic solvents
US2907749A (en) * 1957-07-17 1959-10-06 Sylvan O Greenlee Polyurethane of a polyisocyanate and a self-ester of a hydroxyaryl-aliphatic acid or an acyl derivative thereof
US2921869A (en) * 1956-05-22 1960-01-19 Du Pont Coated polymeric thermoplastic dielectric film
US2929800A (en) * 1951-07-19 1960-03-22 Du Pont Polytetramethylene ether polyurethane polymers
US2968575A (en) * 1953-06-30 1961-01-17 Du Pont Stable polyurethane latex and process of making same
US2971221A (en) * 1959-01-30 1961-02-14 Du Pont Process for curing continuous extrusions of compounded elastomers
US3001973A (en) * 1953-05-23 1961-09-26 Bayer Ag Production of cross-linked plastics
US3007899A (en) * 1958-07-16 1961-11-07 Union Carbide Corp Polyurethane (ester glycol) compositions
US3036878A (en) * 1959-09-25 1962-05-29 Globe Mfg Company Polyurethanes
US3061470A (en) * 1959-04-23 1962-10-30 Deering Milliken Res Corp Sizing textile yarns
US3100721A (en) * 1961-02-21 1963-08-13 Du Pont Process for producing microporous films and coatings
US3115479A (en) * 1955-12-08 1963-12-24 R oconr
US3222322A (en) * 1959-07-08 1965-12-07 Bayer Ag Polyurethane coating compositions

Family Cites Families (7)

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US3015650A (en) * 1957-05-07 1962-01-02 Goodrich Co B F Thermoplastic polyesterurethanes
BE576917A (en)) * 1958-03-22
US3006897A (en) * 1958-11-07 1961-10-31 Armstrong Cork Co Diisocyanate-modified acid-treated polyesters
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Also Published As

Publication number Publication date
NL293352A (en)) 1900-01-01
BE633065A (en)) 1900-01-01
DE1300278B (de) 1969-07-31
SE329887B (en)) 1970-10-26
NL133551C (en)) 1900-01-01
DK111395B (da) 1968-08-12

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